Synthesis of 2-(hetero)arylquinazolinones in aqueous media

Article abstract of DOI:10.24820/ark.5550190.p009.894

Mechanochemical treatment of N-unsubstituted or N-methyl anthranilamide with benzaldehyde yielded their Schiff bases derivatives which could be easily cyclized to the corresponding 2-phenyl-2,3-dihydroquinazolinones via thermal rearrangement in water. On the basis of the above findings, an eco-friendly method was applied to prepare quinazolin-4(1H)-one derivatives from anthranilamides and a number of (hetero)aryl aldehydes. Heating the aqueous mixture of starting compounds to 90 °C resulted in the products in 81-94% yields. All products precipitated from the reaction mixture and were isolated by simply filtration. No further work-up or purification was necessary.

Full text of DOI:10.24820/ark.5550190.p009.894

General Papers
ARKIVOC 2016 (vi) 247-258
Synthesis of 2-(hetero)arylquinazolinones in aqueous media
Magyar Tímeaa, Ferenc Miklósa, László Lázára and Ferenc Fülöpa,b,*
aInstitute of Pharmaceutical Chemistry and bStereochemistry Research Group of the
Hungarian Academy of Sciences, University of Szeged, H-6720 Szeged, Eötvös utca 6, Hungary
E-mail: fulop@pharm.u-szeged.hu
DOI: https://doi.org/10.24820/ark.5550190.p009.894
Abstract
Mechanochemical treatment of N-unsubstituted or N-methyl anthranilamide with benzaldehyde
yielded their Schiff bases derivatives which could be easily cyclized to the corresponding 2-
phenyl-2,3-dihydroquinazolinones via thermal rearrangement in water. On the basis of the above
findings, an eco-friendly method was applied to prepare quinazolin-4(1H)-one derivatives from
anthranilamides and a number of (hetero)aryl aldehydes. Heating the aqueous mixture of starting
compounds to 90 °C resulted in the products in 81–94% yields. All products precipitated from the
reaction mixture and were isolated by simply filtration. No further work-up or purification was
necessary.
Keywords: Environmentally friendly methods, aqueous, mechanochemical, ball-milling
reactions, chromatography-free
Introduction
2,3-Dihydroquinazolines (DHQZ) are effective substances in medicinal chemistry that possess a
broad spectrum of biological activities, including MAO-A1 and Shiga toxin2 inhibitor, diuretic3 or
anti-inflammatory4 activities. Among the various DHQZ derivatives, 2-aryl quinazolinone hybrids
have been found to be good candidates for the inhibition of both tubulin polymerization and the
binding of colchicine to tubulin.5 Incorporation of a pyrazole moiety at position 2 of the
quinazolinone heterocycle gives safer and potent antioxidant6 and insecticidal7 (Spodoptera
frugiperda) agents. Some 2-spirooxindole dihydroquinazolinones demonstrate anti-bacterial
activity in vitro.8
Several methods have been reported for the preparation of 2-substituted 2,3-
dihydroquinazolin-4(1H)-ones,
based
mainly
on
the
cyclocondensation
of
anthranil(onitrile)amides with aldehydes in the presence of various catalysts such as cyanuric
chloride,9 citric acid10, ZnCl2,11 p-TSA12 and sulfamic acid13. Moreover, many of these protocols
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are associated with the application of exotic catalyst systems, extended reaction times and tedious
work-up procedures. For example, some classical and modern methods reported in the literature
for the synthesis of 2-phenyl-2,3-dihydroquinazolin-4-(1H)-one (4a) via the reaction of
anthranilamide (1a) and benzaldehyde (2a) are outlined in Table 1.
Table 1. Synthesis of 2-phenyl-2,3-dihydroquinazolin-4(1H)-one (4a)
Benzaldehyde Isolated
Temp. Time
Entry
Solvent
Catalyst
equiv.
yield
[%]work up
98e,rc
Ref.
[°C]
[h]
0.25
1
14
15
1
2
PEG
25
MCM-41-dtz-Ni
Fe3O4/Cu(II)-
1
1
ethanol
78
99w
Schiff base
Indion-Ina 225 H
16
17
18
3
4
5
methanol
toluene
water
25
2
1
1
1
1
98ch
100–
100e,ch
110
120
18
16
–
–
19
20
6
7
ethanol
78
25
0.83
0.33
Boehmite SSA
96e,rc
1
1
acetonitrile
L-proline nitrate
96rc
1-iPr-1,2,4-
triazol.HOTf
21
22
23
8
9
water
25
MW
40
0.03
96w
98w,rc
98
1
–
0.17
Co-CNTs
dichloromet
hane
48–
72
1.3
10
–
24
25
26
27
28
97e,rc
94rc
93rc
94rc
94rc
1
1
11
12
13
14
15
water
water
ethanol
water
water
70
25
25
70
25
0.58
0.33
1.5
1
MNPs-PSA
Graphene Oxide
Y(OTf)3
0.91
1
SuSa
1
0.3
p-SAC
29
96rc
1
16
water
50
0.42
β-CD-SO3H
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Table 1 (continued)
1
present
work
present
work
17
water
water
90
90
2
1
–
–
91
–
18*
93
ch column chromatography; e extraction; rc recrystallization; w washing with organic solvent; * from
Schiff base 3a
We have previously described eco-friendly methods for the preparation of quinazolin-4(1H)-
ones in aqueous30 or solventless medium from 1a31 or 2-amino-benzhydrazides32 and a number of
aldehydes33 and ketones.34 Inspired by the excellent results of the mechanochemical and in/on
water syntheses, we decided to extend the ring closure of 1a and 2-amino-N-methylbenzamide
(1b) with the reactions of a number of (hetero)aromatic aldehydes under either aqueous or ball-
milling conditions.
Results and Discussion
We initially studied the influence of solventless and catalyst-free conditions in the reaction of
anthranilamides 1a and 1b with benzaldehyde (2a) as model reaction. The liquid–solid
condensations of 1a and 1b with 2a were carried out in a mixing ball-mill. The reactants in a
stoichiometric ratio were placed in a stainless-steel jar with two stainless-steel balls, the vessel was
closed, and milling was started at rt at 25 Hz. After a 1-h milling only 10% of the starting
compounds remained unconsumed (monitored by TLC). Milling was continued for an additional
1 h, during which eutectic melt products were obtained. 1H NMR spectroscopy of crude products
demonstrated that the yields of melt-like compounds were nearly quantitative. Interestingly, under
this reaction condition, mixtures both of kinetic (3a, 3b) and thermodinamic (4a, 5a) products
were formed (Table 2, Entry 1 and 2). Successful separation of the material in the jar was achieved
when the reaction mixtures were dissolved in methanol. After evaporation of methanolic solution
to small volume under reduced pressure at rt, followed by the addition of a mixture of Et2O–n-
1
hexane, crystalline imines 3a and 3b were separated out, characterized by FT-IR and H NMR
13
analysis. The C NMR data on 3a and 3b were described by the utilization of 2D HSQC and
HMBC NMR spectra because of the quick intramolecular cyclization of Schiff bases to 4a and 5a
on standing in d6-DMSO.
Rao et al. reported that intramolecular cyclization of 3b to 5a is facile and apparently an
irreversible process, both in free-state and in acetic acid.36 In view of above observation, we
decided to investigate the rearrangement of 3a and 3b in aqueous medium. After stirring for 1 h at
90 °C, precipitated 4a and 5a were isolated by simple filtration in a yield of 91–93% and high
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purity (97–99%). Compounds were obtained as pale yellow solids, their physical and spectroscopic
data were in good agreement with the literature.21,38
In order to test our in/on water protocol, we first explored cyclization of a stoichiometric amount
of 1a and 1b with 2a at rt. After stirring for 6 h a mixture of 3a/4a or 3b/5a precipitating was
filtered off and dried. The ratio of inseparable mixture of constitutional isomers was determined
by 1H MNR spectroscopy (Table 2, Entry 3 and 4).
Table 2. Condensation of anthranilamides with benzaldehyde under various conditions
Temp.
[° C]
Time
[h]
Product/
(ratio)
Conversion/Yield
Mp.
[° C]
163–165b
(217)35
124–126b
(76)36
Entry
R
H
Solvent
–
[%]
3a : 4a
1
2
3
4
25
25
25
25
2
2
6
6
98a/68(3a)b
97a/61(3b)b
83c
(95 : 5)a
3b : 5a
Me
H
–
(91 : 9)a
3a : 4a
water
water
–
(79 : 21)a
3b : 5a
Me
80c
–
(30 : 70)a
224–226c
(225–
5
6
H
water
water
90
90
2
2
4a
5a
88c
90c
227)37
168–170c
(159–
Me
161)38
Ball-milling at 25 Hz for 2 h; a On the basis of 1H NMR; b From MeOH/Et2O/n-hexane; c From
aqueous suspension.
To optimize the catalyst-free reaction conditions, in addition to the variation in temperature
and reaction time, stirring the starting compounds in water and heating (90 °C, 2 h) were found to
afford the corresponding 4a and 5a in excellent yields and purity (96–98%, Entry 5 and 6).
With a successful procedure available, we further examined the aqueous condensation of 1a
with aldehydes 2b–2j. The mixture of 4 mmol of 1a and 1 equivalent of 4b–4j in 10 ml of water
was stirred at 90 °C for 2–4 h. Cyclic products 4a–4e and 4h–4j were isolated by filtration. Under
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neutral conditions, the corresponding quinazolinones were obtained in 85-94% yields (Table 3).
The poorly water-soluble 2g gave an excellent product yield of 4g only under reflux in a mixture
of ethanol/water (1:2). With slight modification, the reaction of 1a with 2f was complete in the
presence of 1 ml of 1% I2/KI (Lugol’s solution)34 (Entry 6 and 5).
Table 3. Syntheses of 2-(hetero)aryl-2,3-dihydroquinazolin-4(1H)-ones (4b–4j) in aqueous
media
Time
[h]
Yield
[%]a
Mp
[°C]b (lit.)ref
Entry
(Het)Ar
4-MeC6H4
4-FC6H4
Product
4b
4c
229–232
1
2
3
4
5
6
7
8
9
3
3
2
3
4
2
3
3
2
85
92
89
91
88c
90d
94
86
93
(232–234)27
205–207
(203–204)22
209–212
4-ClC6H4
4-BrC6H4
4-CNC6H4
4-NO2C6H4
2-naphthyl
2-furyl
4d
4e
(206–208)20
202–205
(198–199)20
Mp > 320
(350–351)40
194–198
4f
4g
(199–201)39
223–226
4h
4i
(225–226)22
167–170
(167–168)20
230–233
(225–227)41
3-piridyl
4j
a Isolated yields; b from aqueous suspension; c 1 mol% I2/KI; d from EtOH–H2O (1:2);
The products were characterized by their spectral data and melting points. 1H NMR data of the
crude reaction products correlated well with literature values.
Inspired by the successful attempt with 1a, we extended the aqueous cyclocondensation of 2b–2j
with 2-amino-N-methylbenzamide (1 b). All of these reactions were carried out essentially under
the same conditions as described above, except that reaction times were shorter for 5f and 5h
(Table 4, Entry 5 and 7). In the green procedure, N-methyl-quinazolinones 5b–5j were obtained in
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good to excellent yields (81–93%). Products 5b, 5d and 5g were characterized by comparion of
their spectral data and melting points with those reported in the literature. Although 5e42 can be
found as a known chemical substance its physical and spectroscopic properties have not been fully
studied. In this work we report characterization of 5c, 5e, 5f and 5h–j in the Experimental Section.
Table 4. Syntheses of 2-(hetero)aryl-3-methyl-2,3-dihydroquinazolin-4(1H)-one (5b–5j) in
aqueous media
Time
[h]
Yield
[%]a
Mp
[°C]b (lit.)ref
167–169
(150–152)38
200–201
–
Entry
(Het)Ar
4-MeC6H4
4-FC6H4
Product
5b
5c
1
2
3
4
5
6
7
8
9
3
3
2
3
3
2
2
3
2
88
90
93
89
81c
92d
93
89
91
202–204
(196)36
198–200
–
4-ClC6H4
4-BrC6H4
4-CNC6H4
4-NO2C6H4
2-naphthyl
2-furyl
5d
5e
179–182
–
5f
190–194
(196–198)39
219–221
–
5g
5h
5i
156–159
–
177–178
–
3-pyridyl
5j
a Isolated yields; b from aqueous suspension; c 1 mol% I2/KI; dfrom EtOH–H2O (1:2);
In conclusion, we have developed an aqueous green synthesis of known and new 2-
(hetero)aryl-quinazolinones. The condensations of (N-methyl)anthranilamide with
(hetero)aromatic aldehydes proceeded efficiently in/on water to provide a convenient synthesis of
4a–4j or 5a–5j in excellent yields without the need for further work-up. We have also shown that
Schiff bases prepared by high-energy ball milling resulted in heterocycles 4a and 5a in water at
90 °C. This method has a number of advantages over other methods: the reaction techniques are
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very simple, and the syntheses occur under mild, green reaction conditions without the need for
costly, highly sensitive catalysts.
Experimental Section
General Procedures. Products 4a–j, 5a, 5b, 5d and 5g are known compounds and their physical
1
data and H NMR spectra were essentially identical with those of authentic samples. Other
products, which are new, were characterized by IR, 1H, and 13C NMR spectroscopy and elemental
13
analysis. 1H- (400 Hz), C- (100 MHz) and 2D NMR spectra were recorded in d6-DMSO on a
Bruker Avance DRX 400 spectrometer with TMS as internal reference. Analytically pure samples
of 3a, 3b and new compounds (5c, 5e, 5f and 5h–j) were prepared by crystallization from
MeOH/Et2O/n-hexane or EtOH.
Melting points were determined on a Kofler apparatus and are uncorrected. FT-IR spectra were
recorded in KBr pellets on a Perkin-Elmer 100 FT-IR spectrometer. Elemental analyses were
carried out on a Perkin-Elmer 2400 elemental analyser.
The ball-milling experiments were performed in a Retsch MM400 mixer mill with two stainless-
steel balls 15 mm in diameter in a stainless-steel jar (25 mL) at 25 Hz at rt.
Preparation of Schiff bases 3a and 3b
1a or 1b (4.0 mmol), freshly distilled 2a (0.42 g, 0.40 mL, 4.0 mmol) and two stainless-steel balls
15 mm in diameter were placed in a stainless-steel jar. The vessel was vibrated at 25 Hz for 2 h.
The reaction progress was monitored by TLC. 10 mL of MeOH was added to the reaction mixture
in the jar. The suspension was mixed at 25 Hz for 5 min, filtered, the filtrate was evaporated to ca.
2 ml at rt. After addition of 10 mL of Et2O–n-hexane (1 : 1), crystalline products 3a and 3b were
filtered off, washed with diethyl ether (2 mL) and dried. Analytical and spectroscopic data on 3a
and 3b are given below.
2-(Benzylideneamino)benzamide (3a). Pale yellow crystals, mp 163–165 °C (MeOH–Et2O–n-
hexane); IR (cm–1): 3384, 3193, 3054, 2894, 1626, 1591, 1452, 1372, 769; 1H NMR δ (ppm): 7.23
(d, J = 7.8 Hz), 1H, ArH), 7.35 (m, 1 H, ArH), 7.52–7.64 (m, 5H, ArH and NHCO), 7.90–8.00 (m,
3H, ArH), 8.21 (br s, 1H, NHCO), 8.61 (s, 1H, N=CH); 13C NMR (HMBC) δ (ppm): 119.0, 125.7,
128.9 (4×C), 129.8, 131.9, 132.1, 135.4, 149.1, 149.3, 162.2, 167.0; Anal. calcd. for C14H12N2O
(224.26) (%): C, 74.98; H, 5.39; N, 12.49. Found: C, 74.75; H, 5.51; N, 12.21;
2-(Benzylideneamino)-N-methylbenzamide (3b). Pale yellow needles, mp 124–126 °C (MeOH–
1
Et2O–n-hexane); IR (cm–1): 3292, 3064, 3039, 2937, 1631, 1614, 1589, 1394, 750; H NMR δ
(ppm): 2.82 (d, J = 4.8 Hz, 3H, CH3) 7.25 (d, J = 7.6 Hz, 1H, ArH), 7.34 (m, 1H, ArH), 7.49–7.63
(m, 4H, ArH), 7.85 (dd, J = 7.8 Hz, J = 1.3 Hz, 1H, ArH), 7.95–8.00 (m, 2H, ArH), 8.61 (s, 1H,
13
N=CH), 8.65 (br m, 1H, NHCO); C NMR (HMBC) δ (ppm): 25.7, 118.9, 125.5, 128.7 (4×C),
129.8, 131.9, 132.1, 135.4, 148.9, 149.0, 162.0, 166.4; Anal. calcd. for C15H14N2O (238.28) (%):
C, 75.61; H, 5.92; N, 11.76. Found: C, 75.74; H, 5.71; N, 11.51;
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Preparation of quinazolinones 4a and 5a
Schiff base 3a (0.22 g, 1 mmol) or 3b (0.24 g, 1 mmol) was heated in 5 mL of water at 90 °C for
1 h. From the cooled suspension, product 4a or 5a was precipitated, filtered off and dried.
1
2-Phenyl-2,3-dihydroquinazolin-4(1H)-one (4a): white powder, mp 224–226 °C. H NMR
spectrum was identical with that of an authentic sample.
3-Methyl-2-phenyl-2,3-dihydroquinazolin-4(1H)-one (5a): white powder, mp 168–170 °C. H
1
NMR spectrum was identical with that of an authentic sample.
Synthesis of 2-(hetero)aryl-2,3-dihydroquinazolin-4(1H)-ones 4b–4j and 5b–5j. To a stirred
mixture of 1a or 1b (4.0 mmol), and in 10 mL of water (for 4b-e,h,j and 5b-e,h,j) or 10 mL of
water and 1 mL of 1% I2/KI (for 4f and 5f) or in 10 mL of EtOH–water (1 : 2) (for 4g and 5g) 2b–
2j (4 mmol) was added in portions. After vigorous stirring at rt for 10 min the aqueous suspension
was heated at 90 °C for 2–4 h. After cooling to room temperature the precipitates 4b–4j and 5b–
5j were collected by filtration, washed with water (3 mL) and dried. Crude 4b–4j, 5b, 5c and 5g
1
were characterized by the melting points and H NMR spectra. Analytically pure samples of 5c,
5e, 5f and 5h–j were prepared by crystallization from EtOH. Analytical and spectroscopic data of
new compounds are given below.
2-(4-Fluorophenyl)-3-methyl-2,3-dihydroquinazolin-4(1H)-one (5c). Colorless crystals, mp
200–201 °C (EtOH); IR (cm–1): 3292, 3113, 3064, 2939, 2820, 1633, 1613, 1508, 1488, 1391,
1225, 753; 1H NMR δ (ppm): 2.84 (s, 3H, CH3), 5.85 (d, J = 2.3 Hz, CH), 6.61–6.70 (m, 2H, ArH),
7.16–7.24 (m, 3H, ArH), 7.28 (d, J = 2.2 Hz, 1H, NH), 7.33–7.41 (m, 2H, ArH), 7.65 (dd,
J = 7.7 Hz, J = 1.5 Hz, 1H, ArH); 13C NMR δ (ppm): 31.8, 71.3, 114.1, 114.3, 115.3, 115.5, 117.0,
127.3, 128.2, 128.3, 133.2, 136.9 (2×C), 146.2, 160.8, 162.4, 163.3; Anal. calcd. for C15H13FN2O
(256.27) (%): C, 70.30; H, 5.11; N, 12.49. Found: C, 70.55; H, 5.21; N, 12.30;
2-(4-Bromophenyl)-3-methyl-2,3-dihydroquinazolin-4(1H)-one (5e). Colorless crystals, mp
198–200 °C (EtOH); IR (cm–1): 3292, 3064, 2935, 2819, 1633, 1612, 1594, 1485, 1390, 756; 1H
NMR δ (ppm): 2.86 (s, 3H, CH3), 5.84 (d, J = 2.4 Hz, CH), 6.61–6.70 (m, 2H, ArH), 7.18–7.30
(m, 3H, ArH), 7.32 (d, J = 2.3 Hz, 1H, NH), 7.54–7.59 (m, 2H, ArH), 7.65 (dd, J = 7.8 Hz,
13
J = 1.5 Hz, 1H, ArH); C NMR δ (ppm): 32.0, 71.2, 114.1, 114.3, 117.1, 121.6, 127.3, 128.2
(2×C), 131.5 (2×C), 133.2, 140.0, 146.1, 162.4; Anal. calcd. for C15H13BrN2O (317.18) (%): C,
56.80; H, 4.13; N, 8.83. Found: C, 56.58; H, 4.21; N, 8.50;
4-(1,2,3,4-Tetrahydro-3-methyl-4-oxo-2-quinazolyl)-benzonitrile (5f). Colorless crystals, mp
1
179–182 °C (EtOH); IR (cm–1): 3330, 3056, 2930, 2229, 1634, 1612, 1506, 1487, 1392, 751; H
NMR δ (ppm): 2.91 (s, 3H, CH3), 5.96 (d, J = 2.6 Hz, CH), 6.60–6.71 (m, 2H, ArH), 7.21 (m, 1H,
ArH), 7.44 (d, J = 2.5 Hz, 1H, NH), 7.46–7.52 (m, 2H, ArH), 7.66 (dd, J = 7.8 Hz, J = 1.3 Hz,
13
1H, ArH), 7.80–7.88 (m, 2H, ArH); C NMR δ (ppm): 32.2, 71.2, 111.2, 114.2, 114.4, 117.3,
118.4, 127.0 (2×C), 127.4, 132.6 (2×C), 133.4, 145.9 (2×C), 162.3; Anal. calcd. for C16H13N3O
(263.29) (%): C, 72.99; H, 4.98; N, 15.96. Found: C, 73.18; H, 5.21; N, 15.70;
3-Methyl-2-(2-naphthalenyl)-2,3-dihydroquinazolin-4(1H)-one (5h). Colorless crystals, mp
219–221 °C (EtOH); IR (cm–1): 3350, 3062, 2909, 1624, 1609, 1519, 1486, 1390, 821, 757, 750;
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1H NMR δ (ppm): 2.91 (s, 3H, CH3), 6.01 (s, 1H, CH), 6.62–6.72 (m, 2H, ArH), 7.21 (m, 1H,
ArH), 7.38 (s, 1H, NH), 7.47–7.58 (m, 3H, ArH), 7.71 (dd, J = 8.0 Hz, J = 1.5 Hz, 1H, ArH), 7.79
(m, 1H, ArH), 7.86–7.96 (m, 3H, ArH); 13C NMR δ (ppm): 31.9, 72.3, 114.0, 114.3, 117.0, 124.0,
125.1, 126.4, 126.5, 127.4, 127.5, 127.9, 128.6, 132.4, 132.9, 133.2, 137.9, 146.4, 162.6; Anal.
calcd. for C19H16N2O (288.34) (%): C, 79.14; H, 5.59; N, 9.72. Found: C, 79.18; H, 5.31; N, 9.83;
2-(2-Furanyl)-3-methyl-2,3-dihydroquinazolin-4(1H)-one (5i). Pale red–brown crystals, mp
156–159 °C (EtOH); IR (cm–1): 3237, 3128, 3103, 3060, 3028, 2918, 1626, 1612, 1524, 1485,
1399, 1151, 1138, 1014, 914, 882, 749; 1H NMR δ (ppm): 2.97 (s, 3H, CH3), 5.90 (d, J = 2.8 Hz,
1H, CH), 6.22 (d, J = 3.3 Hz, 1H, furyl-H), 6.36 (m, 1H, furyl-H), 6.66–6.78 (m, 2H, ArH), 7.24
(m, 1H, ArH), 7.36 (d, J = 2.5 Hz 1H, NH), 7.58 (m, 1H, furyl-H), 7.67 (m, 1H, ArH); 13C NMR
δ (ppm): 32.0, 66.0, 107.4, 110.2, 114.3, 114.8, 117.3, 127.3, 133.1, 143.0, 146.4, 153.0, 162.5;
Anal. calcd. for C13H12N2O2 (228.25) (%): C, 68.41; H, 5.30; N, 12.27. Found: C, 68.58; H, 5.39;
N, 12.03;
3-Methyl-2-(3-pyridinyl)-2,3-dihydroquinazolin-4(1H)-one (5j). Colorless crystals, mp 177–
178 °C (EtOH); IR (cm–1): 3283, 3058, 3034, 2999, 2932, 2821, 1634, 1613, 1594, 1579, 1504,
1486, 1418, 1390, 782, 767; 1H NMR δ (ppm): 2.89 (s, 3H, CH3), 5.94 (d, J = 2.6 Hz, 1H, CH),
6.62–6.73 (m, 2H, ArH), 7.22 (m, 1H, ArH), 7.35–7.41 (m, 2H, pyridyl-H and NH), 7.64–7.70 (m,
2H, pyridyl- and ArH), 8.50–8.56 (m, 2H, pyridyl-H, ArH); 13C NMR δ (ppm): 32.0, 70.0, 114.3,
114.5, 117.4, 123.7, 127.4, 133.3, 133.6, 135.9, 146.1, 147.6, 149.7, 162.5; Anal. calcd. for
C14H13N3O (239.27) (%): C, 70.28; H, 5.48; N, 17.56. Found: C, 70.58; H, 5.21; N, 17.42;
Acknowledgements
We are grateful to the Hungarian Research Foundation (OTKA K-115731) for financial support.
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